质子耦合电子转移反应动力学的理论研究
Theoretical study of kinetics of proton coupled electron transfer in photocatalysis
摘要：
太阳光催化是环境保护、太阳能转化和可持续燃料生产的最有前途的方法之一。计算建模是一个快速发展的领域，需要适应和进一步发展现有的理论工具。质子和电子的耦合转移是质子交换过程中的一个重要反应。在这项工作中，我们提出了我们的方法发展的第一步，我们应用现有的动力学理论，这种耦合转移到一个模型系统，即甲醇光解金红石TiO $_2$（110）表面，与高层次的第一性原理计算的帮助下。此外，我们适应Stuchebrukhov-Hammes-Schiffer动力学理论，在那里我们使用Georgievskiii-Stuchebrukhova振动耦合，计算质子耦合电子转移反应的速率常数为一个特定的途径。特别是，我们提出了一个修改后的表达式来计算质子隧穿过程中的振动波函数的近共振条件的速率常数。
英文摘要：
Photocatalysis induced by sunlight is one of the most promising approach to environmental protection, solar energy conversion and sustainable production of fuels. The computational modeling of photocatalysis is a rapidly expending field which requires to adapt and further develop the available theoretical tools. The coupled transfer of proton and electron is an important reaction during photocatalysis. In this work, we present the first step of our methodology development in which we apply existing kinetic theory of such coupled transfer to a model system, namely, methanol photo-dissociation on rutile TiO$_2$(110) surface, with the help of high-level first-principles calculations. Moreover, we adapt the Stuchebrukhov-Hammes-Schiffer kinetic theory, where we use the Georgievskii-Stuchebrukhova vibronic coupling, to calculate the rate constant of the proton coupled electron transfer reaction for a particular pathway. In particular, we propose a modified expression to calculate the rate constant which enforces the near-resonance condition for the vibrational wavefunction during proton tunneling.
机构、总结、中文摘要均由AI分析而来，可能存在错误，请以论文正文为准。
